2007

A metallanaphthalyne complex from zinc reduction of a vinylcarbyne complex

Cl prevents insertion: The first metallanaphthalyne 2 has been obtained by Zn reduction of Os carbyne complex 1. The key to its isolation was the use of o-chlorophenyl instead of phenyl substituents to avoid formation of a putative hydrido metallanaphthalyne intermediate (supported by DFT calculations), which undergoes migratory insertion of the carbyne into the OsH bond and rearrangement to give an indenyl complex as the final product.

Ligand effect on the insertion reactions of allenes with MHCl(CO)(PPh3)(3)and MHCl(PPh3)(3) (M = Ru, Os)

Treatment of RuHCl(CO)(PPh3)(3) with CH2=C=CHCO2Me gives the allyl complex Ru(77 3 -CH2CHCHCO2Me)CI(CO)(PPh3)(2). The analogous allyl complexes Os(eta(3)-CH2CHCHR)Cl(CO)(PPh3)(2) (R = Ph, CH2Ph) are also produced from the reactions of OsHCI(CO)(PPh3)(3) with CH2=C=CHR. In contrast, MHCl(PPh3)(3) (M = Ru, Os) react with CH2=C=CHR to give the vinyl complexes MCl((C(CH3)=CHR)(CH2 C=CHR)(PPh3)(2) (M = Ru, R = CMe3, M = Os, R = CMe3, Ph, CO2Et).

Understanding nonplanarity in metallabenzene complexes

The nonplanarity found in metallabenzene complexes has been investigated theoretically via density functional theory (DFT) calculations. A metallabenzene has four occupied π molecular orbitals (8 π electrons) instead of three that benzene has. Our electronic structure analyses show that the extra occupied π molecular orbital, which is the highest occupied molecular orbital (HOMO) in many metallabenzenes, has antibonding interactions between the metal center and the metal-bonded ring-carbon atoms, providing the electronic driving force toward nonplanarity.